US20010010807A1 - Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery - Google Patents
Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery Download PDFInfo
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- US20010010807A1 US20010010807A1 US09/242,308 US24230899A US2001010807A1 US 20010010807 A1 US20010010807 A1 US 20010010807A1 US 24230899 A US24230899 A US 24230899A US 2001010807 A1 US2001010807 A1 US 2001010807A1
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- general formula
- complex oxide
- heating
- slurry
- spray
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Links
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 70
- 229910052759 nickel Inorganic materials 0.000 title description 12
- 229910052744 lithium Inorganic materials 0.000 title description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 5
- 229910017052 cobalt Inorganic materials 0.000 title description 2
- 239000010941 cobalt Substances 0.000 title description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 2
- 239000006182 cathode active material Substances 0.000 title 1
- 239000002131 composite material Substances 0.000 title 1
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 32
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims description 51
- 239000002002 slurry Substances 0.000 claims description 47
- 239000011164 primary particle Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 37
- -1 basic metal salt Chemical class 0.000 claims description 33
- 239000007921 spray Substances 0.000 claims description 33
- 229910052728 basic metal Inorganic materials 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 26
- 150000002642 lithium compounds Chemical class 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 239000012736 aqueous medium Substances 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- 239000011163 secondary particle Substances 0.000 claims description 12
- 150000001639 boron compounds Chemical class 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims 1
- 239000002609 medium Substances 0.000 claims 1
- 229910003005 LiNiO2 Inorganic materials 0.000 abstract description 12
- 238000007599 discharging Methods 0.000 abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 239000000047 product Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- 239000011572 manganese Substances 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000000725 suspension Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000000634 powder X-ray diffraction Methods 0.000 description 15
- 229910002651 NO3 Inorganic materials 0.000 description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 12
- 239000004327 boric acid Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- 229910021441 lithium nickel cobalt complex oxide Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910011715 LiNi0.80 Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910021440 lithium nickel complex oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- UEPVQVKBYZCVJN-UHFFFAOYSA-N B(O)(O)O.B(O)(O)O.B(O)(O)O.B(O)(O)O.[Li] Chemical compound B(O)(O)O.B(O)(O)O.B(O)(O)O.B(O)(O)O.[Li] UEPVQVKBYZCVJN-UHFFFAOYSA-N 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910011419 LiNi0.80Co0.10Al0.10O2 Inorganic materials 0.000 description 1
- 229910015332 LiNi0.80Co0.20O2 Inorganic materials 0.000 description 1
- 229910017016 Ni0.8Co0.15 Inorganic materials 0.000 description 1
- 229910015468 Ni1-xCox Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 101100313003 Rattus norvegicus Tanc1 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a lithium nickel cobalt complex oxide having a high purity, a high crystallinity, a high battery capacity and stable structure so that the degree of decrease in the capacity is little even with increasing the number of charging and discharging cycle, to a process for preparing the same, and to a positive electrode active material for a secondary battery.
- LiNiO 2 and LiCoO 2 which are layered compounds capable of intercalating and deintercalating lithium ion. Of them, LiNiO 2 is being expected owing to its higher electric capacity than LiCoO 2 .
- LiNiO 2 has not yet been put to practical use because it has problems in the charging and discharging cycle characteristics, the storage stability and the stability at a high temperature . Only LiCoO 2 has been practically used as the positive electrode active material.
- LiNiO 2 has been prepared by mixing lithium components (LiOH, Li 2 CO 3 , LiNO 3 etc.) with nickel components (hydroxide, carbonate etc.) in a dry state and thereafter subjecting the mixture to the reaction, and hence the heating at an elevated temperature for a long time was required. Consequently, the crystal growth proceeds but some of lithium is evaporated off and NiO as a by-product is formed, thereby the lowering of the purity is caused.
- An object of the present invention is to provide a novel lithium nickel cobalt complex oxide which has improved properties with respect to the above faults of the hitherto known LiNiO 2 and its related complex oxide, namely which has a high purity, a high crystallinity, a high battery capacity and stable structure so that the degree of decrease in the capacity is little even by increasing the number of charging and discharging cycle.
- Another object of the present invention is to provide a process for preparing said lithium nickel cobalt complex i oxide by a process via wet process which is different from the hitherto known dry process whereby the size of the formed spherical and secondary and primary particle may be set to a desired.
- a further other object of the present invention is to provide a positive electrode active material for a lithium ion secondary battery containing as an effective component said lithium nickel cobalt complex oxide.
- M represents at least one element selected from the group consisting of Al, Fe, Mn and B
- y represents 0.9 ⁇ y ⁇ 1.3
- x 1 +x 2 x
- x represents 0 ⁇ x ⁇ 0.5
- x 1 represents 0 ⁇ x 1 ⁇ 0.5
- x 2 represents 0 ⁇ x 2 ⁇ 0.3
- M is B
- X 2 represents 0 ⁇ x 2 ⁇ 0.1
- M is a combination of B and at least one element among Al, Fe and Mn
- x 2 represents 0 ⁇ x 2 ⁇ 0.3 wherein the proportion of B is a range of from 0 to 0.1.
- novel complex oxide of the present invention has the following features.
- the first feature lies in the composition represented by the above general formula (I) based on which with holding as high battery capacity as LiNiO 2 , not only its faults i.e. cycle property (deterioration of discharge capacity caused by increasing the number of cycle) and high temperature stability may be improved but also the amount used of an expensive cobalt may be suppressed to the minimum thereby economical merit may be realized.
- the second feature of the complex oxide lies in that it has a high crystallinity and a high purity as identified by its X -ray diffraction pattern. That is, it is highly purified complex oxide to such extent that X- ray diffraction pattern shows that a ratio in the peak intensity of the face ( 003 ) to the face ( 104 ) i.e., ( 003 ) /( 104 ) is 1.2 or higher and a ratio in the peak intensity of the face ( 006 ) to the face ( 101 ) i.e., ( 006 )/( 101 ) is 0.13 or lower, said face being defined by Miller indices hkl, the proportion of (Ni 3 ⁇ +Co 3.
- the total (Ni +Co) being 99% by weight or higher, a BET specific surface area being 0.1 ⁇ 2 m 2 /g, an average secondary particle size D being in the range of 5 ⁇ 100 ⁇ m with 10% of the particle size distribution being 0.5 D or higher and 90% 2 D or lower, the surface of the spherical secondary particle being uneven as observed with a scanning electron microscope (SEM) and the primary particle constituting the spherical secondary particle being in the range of 0.2 ⁇ 30 ⁇ m in terms of long diameter with the average diamter of 0.3 ⁇ 30 ⁇ m as observed with a SEM.
- SEM scanning electron microscope
- the lithium nickel cobalt complex oxide of the present invention can be kept in high purity, in spite of being one doped with at least one element selected from the group of consisting of Al, Fe, Mn and B. As shown in Examples described later, the interlayer distance may be efficiently shortened especially by using Co together with Al and /or B whereby the structural instability of Ni by reversible deintercalation of lithium ion can be avoided.
- the greatest feature of the present invention is that Co and at least one element selected from the group of consisting of Al, Fe, Mn and B may be doped as solid solution in a small amount and uniformly into the lithium nickel complex oxide.
- Such lithium nickel cobalt complex oxide of the present invention can be obtained as the composition having a high purity and a high crystallinity by the wet process as described later.
- the third feature of the complex oxide of the present invention is that there can be obtained uniform and primary particle and that shape and size of the secondary paricle may be adjusted to the desired.
- the size of the primary particle is important for a layered compound represented by LiMO 2 in the light of the reversible deintercalation of lithinm ion. Finer the primary particle, better ionic conductivity in the inside of the solid and lithium ion is more reversibly deintercalatable with the outside.
- the present inventors have succeeded in the preparation of the complex oxide having an uniform primary particles of such that a long diameter of the primary particles is in the range of 0.2 ⁇ 30 ⁇ m, preferably 1 ⁇ 20 ⁇ m by combined wet process-spray (or freeze) drying process-press molding and heating processes as described later.
- a complex oxide wherein both the primary and secondary particles are uniform may be prepared by employing especially spray drying-heating processes.
- a long diameter of the primary particles is in the range of 0.2 ⁇ 30 ⁇ m, preferably 1 ⁇ 20 ⁇ m and its average size is in the range of 0.3 ⁇ 30 ⁇ m when observed with a SEM.
- An average size D of the spherical secondary particle formed by spray drying-heating processes is in the range of 5 ⁇ 300 ⁇ m, preferably 5 ⁇ 100 ⁇ m, more preferably 5 ⁇ 20 ⁇ m and the particle is uniform to such extent that 10% of the particle size distribution is 0.5 D or higher and 90% 2D or lower, and the surface of the spherical secondary particle is uneven as can be seen under observation of a SEM.
- the particle ratio (a ratio of the long diameter to the short diameter) of the spherical secondary particles when observed with a SEM lies in the range of a maximum of 1.5 or less and an average of 1.2 or less with 90% or more of them being distributed in 1.3 or less, indicating that they are uniform particles even when there was included some particles having slightly larger particle ratio than defined above in the complex oxide prepared by pulverization after the heating.
- the size of the spherical secondary particles can be set to the range of from 5 ⁇ m to 100 ⁇ m as desired. However, an average size of about 5 ⁇ 30 ⁇ m is desirable for use as the battery material from the viewpoint of processibility. Also, the BET specific surface area lies in the range of 0.1 ⁇ 2 m 2 /g. When it was used as the battery material, since there is no increase in the viscosity of an electrolyte the lowering in conductivity is not caused.
- the average long diameter of the primary particle may be more simply and conveniently achieved by subjecting the spray (or freeze) dried product as above-mentioned to press molding.
- the primary particle is large, it has physical properties that the purity and the crystallinity are high and that the high temperature stability is excellent, and therefore it may be preferably used as the positive electrode active material for a secondary battery which would be used under a severe condition.
- the bulk density becomes large due to press molding applied. That bulk density is high is plus for elevation of the battery capacity.
- said complex oxide may be prepared by adding-an amount of a lithium compound corresponding to the number of atomic moles of Li indicated by y to a basic metal salt represented by the general formula (II)
- M represents at least one element selected from the group consisting of Al, Fe and Mn
- x represents 0 ⁇ x ⁇ 0.5
- x is 0 ⁇ x 1 ⁇ 0.5
- x 2 represents 0 ⁇ x 2 ⁇ 0.3
- x 1 +x 2 x
- n represents 0 ⁇ x ⁇ 0.5
- x represents 0 ⁇ x 1 21 0.5
- N represents at least one element of Al, Fe and Mn
- M in the general formula (I) contains both the N and B
- x represents 0 ⁇ x ⁇ 0.5
- x 1 represents 0 ⁇ x 1 ⁇ 0.5
- x 3 represents 0 ⁇ x 3 ⁇ 0.3 ⁇ x 4
- x 1 +x 3 +x 4 x
- z and m represent positive numbers respectively satisfying the ranges of 0.03 ⁇ z ⁇ 0.3, 0 ⁇ m ⁇ 2] in an aqueous medium, to form a slurry, spray or freeze drying the formed slurry and heating the spray or freeze dried product at a temperature of about 600° C. ⁇ 900° C. for 4 hours or more in an oxidative atmosphere.
- the water soluble lithium compound and the basic metal salt which may be represented by the general formulae (II) , (III) or (IV) (hereinafter, referred to as “the basic metal salt” collectively), there may be employed one each containing an anion which is evaporated off during the heating.
- lithium compound there may be selected one or more from among LiOH, LiNO 3 Li 2 CO 3 and hydrates thereof.
- boric acid and lithium tetraboric acid may be preferably employed.
- a n- in the basic metal salt there may be selected from among the anions shown by NO 3 , Cl , Br - , CH 3 COO - , CO 3 2- and SO 4 2- .
- LiOH as the lithium compound, boric acid as the boron compound and a basic metal salt wherein an anion is nitrate ion are used from the viewpoint of yield, reactivity, effective utilization of the resources and oxidation accelerating effect.
- the combination of these 3 kinds of compounds is particularly preferred from the viewpoint of battery characteritics.
- the basic metal salt which may be employed in the present invention, is preferable the basic salt having a specific composition that size of the primary particle is as fine as below 0.1 ⁇ m when measured by the Scherrer's method.
- this fine particle has a BET specific surface area of 10 m 2 /g or higher, preferably 40 m 2 /g or higher, more preferably 100 m 2 /g or higher.
- BET specific surface area if it is measured after the basic metal salt in an aqueous solution has been dried, as the very fine primary particles aggregates during dry process, then BET specific surface area of the aggregate is measured. If aggregation power is strong, nitrogen gas cannot enter into it and the value of BET specific surface area becomes small. Accordingly the basic metal salt which is practically reacted with a lithium compound in aqueous solution shows a high BET specific surface area so that the surface is highly reactive.
- the basic metal salt having such specific composition has a layered structure, and the chemical composition and the crystal structure where M is at least one of Al, Fe and Mn are similar to those of hydroxide of Ni 1-x Co x1 M x2 .
- the chemical composition and the crystal structure where M is B are similar to those of hydroxide of Ni 1-x Co x 1 .
- the chemical composition and the crystal structure where M is the combination of B and at least one of Al, Fe and Mn are similar to those of hydroxide of Ni 1 Co x1 Ni x3 .
- the basic metal salt is microcrystalline whose surface is highly active. When it is reacted with a lithium compound such as LiOH, an extremely desirable precursor of Li y Ni 1-x Co x1 M x2 O 2 is formed.
- the basic metal salt to be used in the present invention can be prepared by adding an amount of about 0.7 ⁇ 0.95 equivalent, preferably about 0.8 ⁇ 0.95 equivalent of an alkali based on Ni 1-x Co x1 N x3 salt, Ni 1 x Co x1 salt or Ni 1-x Co x1 N x3 salt under the condition below about 80° C. to effect the reaction.
- the alkali to be used in the reaction include alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, amines and the like.
- this basic metal salt is matured at 20 ⁇ 70° C. for 0.1 ⁇ 10 hours after its preparation. Subsequently, any by-products are removed by washing with water and the lithium compound is added, and the boron compound is further added for the purpose of preparing a complex oxide containing B.
- spray or freeze drying method For drying the slurry obtained by such a reaction, spray or freeze drying method is desirable.
- the spray drying method where drying can be instantaneously accomplished and the spherical particles can be obtained is preferred from the viewpoint of the spherical granulation nature and the uniformity of the composition (in dry process requiring some drying time, lithium migrates into the surface of particles to give a non-uniform composition).
- the heating is effected at a temperature of 600° C. ⁇ 800° C., preferably 700° C. ⁇ 750° C. for 4 hours or higher, preferably about 4 - 72 hours, more preferably about 4 ⁇ 20 hours under an oxidative atmosphere (under the flow of oxygen). If the heating time is 72 hours or, more, not only it makes cost up but also it causes evaporation of Li thereby the proportion of trivalent (Ni+Co) to the total (Ni+Co) becomes rather low and the purity becomes bad.
- the second process is press molding process which is advantageous for the purpose of making the primary particle large and further making the bulk density high.
- the dry product obtained by the spray drying or freeze drying process above-mentioned is press molded and then heated, whereby not only the size of the primary particle may be optionally set within the range of 1 - 30 ⁇ m, but also there can be obtained the complex oxide having high bulk density, degree of crystallization and purity.
- the spherical particle that is the spray dried product is excellent powder with respect to flowability, molding and filling properties, and is a good material to be pressed into a shape as it is according to the conventional manner.
- the pressure for molding may be varied depending on the pressing machine to be applied and the amount to be fed and is not limited particularly, usually about 500 ⁇ 3,000 kg/cm 2 is suitable.
- Pressing machine to be applied is not limited particularly and it may be one capable of pressing. However, tablet compressing machine, briquette, roller compactor may be suitably employed.
- the density of the press molded product may be about 1 ⁇ 4g/cc, preferably about 2 ⁇ 3g/cc.
- the press molding is very useful in that moving distance among molecules becomes short and crystal growth during the heating is accelerated. Accordingly, it is not always necessary that the material to be subjected to the press molding is spray dried spherical particle product. The freeze dried product may also be used.
- This press molded product can be heated as it is.
- the heating is effected at a temperature of usually 600 ⁇ 900° C. , preferably 700° C. ⁇ 800° C. for a period of 4 hours or higher, preferably 10 ⁇ 72 hours under an atmosphere of oxygen.
- the heating time is determined depending on the desired size of the primary particle.
- heating in a short time 2 times heating of pre-heating and after-heating may be applied.
- the slurry obtained by the process described previously is spray- or freeze-dried and the spray- or freeze-dried product is first pre-heated at a temperature of about 600° C. ⁇ 900° C. for 0.5 hour or more (preferably 0.5 ⁇ 4 hours) under an oxidative atmosphere, the obtained pre-heating product is pulverized if necessary and pressed into a shape, and then after-heated at a temperature of about 600° C. ⁇ 900° C. for 1 hour or more (preferably 4 ⁇ 48 hours) under an oxidative atmosphere, The total time requird for the heating may be shortened by employing this process.
- the thus obtained complex oxide of the present invention which may be represented by the general formula ( I) retains high battery capacity of 160 ⁇ 180 mAh/g even after 100 charging and discharging cycles and has an improved high temperature cycle property (stability) as is apparent from the Examples described later, and hence it may be effectively utilized as a positive electrode active material for a secondary battery.
- FIG. 1 is powder X -ray diffraction patterns of the complex oxides obtained in Examples 1 ⁇ 4 and Comparative Examples 1 ⁇ 2, respectively.
- FIG. 2 is SEM photograph ( ⁇ 1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 1.
- FIG. 3 is SEM photograph ( ⁇ 1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 4.
- FIG. 4 is powder X -ray diffraction pattern of the complex oxide obtained in Example 5.
- FIG. 5 is powder X - ray diffraction pattern of the complex oxide obtained in Example 6.
- FIG. 6 is powder X -ray diffraction pattern of the complex oxide obtained in Example 7.
- FIG. 7 is SEM photogragh ( ⁇ 30,000) of the complex oxide obtained in Example 5.
- FIG. 8 is SEM photograph ( ⁇ 3,000 magnifications) indicating the primary particles of the complex oxide obtained in Example 6.
- FIG. 9 is SEM photograph ( ⁇ 10,000 magnifications) indicating the primary particles of the complex oxide obtained in Example 7.
- FIG. 10 is powder X -ray diffraction pattern of the complex oxide obtained in Example 8.
- FIG. 11 is powder X -ray diffraction pattern of the complex oxide obtained in Example 9.
- FIG. 12 is powder X -ray diffraction pattern of the complex oxide obtained in Example 10.
- FIG. 13 is powder X -ray diffraction pattern of the complex oxide obtained in Example 11.
- FIG. 14 is SEM photograph ( ⁇ 1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 8.
- FIG. 15 is SEM photograph ( ⁇ 1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 10.
- FIG. 16 is SEM photograph ( ⁇ 1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 11.
- reaction product overflowed from the reaction vessel during the continuous reaction was collected in the receiver tanc.
- the reaction was completed when the necessary amount of the reaction product was collected.
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0. 8 Co 0 19 (OH) 1 833 (NO 3 ) 0 147 ⁇ 0.16 H 2 O) and suspended in water. And then, boric acid was added to the suspension in an amount such that the molar ratio of Ni:Co:B became 80:19:1 with respect to the Ni and Co contents in the suspention. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni +Co+B) became 1.05.
- reaction mixture was spray-dried.
- the obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company)
- the chemical composition of the heating product was LiNi 0. 80 Co 0.19 B 0.01 O 2 .
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.8 Co 0.195 (OH) 1.86 (NO 3 ) 0.130 ⁇ 0. 22 H 2 O) and suspended in water. And then, boric acid was added to the suspension in such amount that the molar ratio of Ni:Co:B became 80:19.5:0.5 with respect to the Ni and Co contents in the suspension. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni +Co+B) became 1.05. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- TF-630 type a product of Yamada Electric Company
- the chemical composition of the heating product was LiNi 0. 80 Co 0. 195 B 0. 005 O 2 .
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.8 Co 0.18 (OH) 1.79 (NO 3 ) 0.17 ⁇ 0.3 H 2 O) and suspended in water. And then, boric acid was added to the suspension in such amount that the molar ratio of Ni Co:B became 80:18:2 with respect to the Ni and Co contents in the suspension. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni+Co
- TF-630 type a product of Yamada Electric Company
- the chemical composition of the heating product was LiNi 0.80 Co 0.18 B 0.02 O 2 .
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.8 Co 0.15 (OH) 1.76 (NO 3 ) 0.14 ⁇ 0.25 H 2 O) and suspended in water. And then, boric acid was added to the suspension in such amount that the molar ratio of Ni Co:B became 80:15:5 with respect to the Ni and Co contents in the suspension. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni+Co+B) became 1.05. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- TF-630 type a product of Yamada Electric Company
- the chemical composition of the heating product was LiNi 0.80 Co 0.15 B 0.05 O 2 .
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.8 Co 0.01 (OH) 1.68 (NO 3 ) 0.12 ⁇ 0.19 H 2 O) and suspended in water. And then, boric acid was added to the suspension in such amount that the molar ratio of Ni Co:B became 80:10:10 with respect to the Ni and Co contents in the suspension. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni+Co+B) became 1.05. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- TF-630 type a product of Yamada Electric Company
- the chemical composition of the heating product was LiNi 0.80 Co 0.10 B 0.10 O 2 .
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.. 8 Co 0.2 (OH) 1.87 (NO 3 ) 0 13 ⁇ 0.14 H 2 O) and suspended in water. And then, 3.0 M aqueous lithium hydroxide solution was added dropwisely to the suspension in an amount such that the molar ratio of Li/(Ni+Co) became 1.05. Thereafter, the reaction mixture was spray dried.
- the obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- the chemical composition of the firing product was LiNi 0.80 Co 0.20 O 2 .
- the chemical composition of the heat-treated product was LiNi 0.80 Co 0.19 B 0.01 O 2 .
- Example 1 99.8 0.1 1.310 0.101 15.21 0.72
- Example 2 99.7 0.2 1.304 0.102 17.21 0.65
- Example 3 99.9 0.1 1.273 0.111 18.01 0.62
- Example 4 99.1 0.1 1.211 0.106 16.42 0.68 Comparative 89.5 0.2 0.873 0.268 17.21 0.61
- Example 1 Comparative 99.6 0.1 1.245 0.104 18.21 0.67
- Example 2
- table 3 shows the results of the battery test (charge and discharge test) conducted according to Experimental Example 4 using the respective complex oxides of Examples 1 ⁇ 4 and Comparative Examples 1 ⁇ 2 to evaluate initial discharge capacity (mAh/g), discharge capacity at 100th cycle (mAh/g) and decrease rate of discharge capacity at 100th cycle (%).
- initial discharge capacity mAh/g
- discharge capacity at 100th cycle mAh/g
- decrease rate of discharge capacity at 100th cycle %.
- the complex oxides of Examples 1 ⁇ 4 were recognized to have the improved cycle characteristics and initial discharge capacity.
- Example 1 (mAh/g) (mAh/g) (%) Example 1 187 182 2.7 Example 2 185 174 5.9 Example 3 184 178 3.3 Example 4 178 167 6.2 Comparative 152 89 41.4 Example 1 Comparative 184 171 9.3 Example 2 Comparative 163 112 31.2 Example 3
- the obtained reaction mixture was filtered, washed with water and suspended in water thereby obtaining a Ni 0 80 Co 0.10 Al 0.10 (OH) 1.7 (NO 3 ) 0.40 slurry.
- a 3.0 mol/l aqueous lithium hydroxide solution was added dropwisely to the obtained slurry in an amount such that the atomic ratio of Li/(Ni+Co+Al) was 1.05 with respect to the (Ni+ Co+Al) content in the above slurry to effect reaction.
- the reaction mixture was spray dried.
- the obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace, and pulverized in a mortar to obtain powdery LiNi 0. 797 Co 0.101 Al 0.102 O 2 .
- the obtained reaction mixture was filtered, washed with water and suspended in water thereby obtaining a Ni 0 80 Co 0.15 Al 0.05 (OH) 1.7 (NO 3 ) 0.35 slurry.
- a 3.0 mol/l aqueous lithium hydroxide solution was added dropwisely to the obtained slurry in an amount such that the atomic ratio of Li/(Ni+Co+Al) was 1.05 with respect to the (Ni+ Co+Al) content in the above slurry to effect reaction.
- the reaction mixture was spray dried.
- the obtained dry gel was pressed into a pellet having ⁇ 14 and a thickness of 2 mm under pressure of 2 t/cm 2 using a static compressor.
- the pellet was put in an alumina boat and heated at 750° C. for 48 hours in an atmosphere of oxygen in a tube furnace, and pulverized in a mortar to obtain powdery LiNi 0.785 Co 0.151 Al 0.054 O 2 .
- the obtained reaction mixture was filtered, washed with water and suspended in water thereby obtaining a Ni 0 80 Co 0.15 Al 0.05 (OH) 1.7 (NO 3 ) 0.35 slurry.
- a 3.0 mol/l aqueous lithium hydroxide solution was added dropwisely to the obtained slurry in an amount such that the atomic ratio of Li/(Ni+Co+Al) was 1.05 with respect to the (Ni+ Co+Al) content in the above slurry to effect reaction.
- the reaction mixture was freeze dried.
- the obtained dry gel was pressed into a pellet having ⁇ 14 and a thickness of 2 mm under pressure of 2 t/cm 2 using a static compressor.
- the pellet was put in an alumina boat and heated at 750° C. for 48 hours in an atmosphere of oxygen in a tube furnace, and pulverized in a mortar to obtain powdery LiNi 0.789 Co 0.151 Al 0.051 O 2 .
- the ratio of the trivalence in (Ni+Co) and the physical properties such as BET specific surface area, the peak intensity ratios (003)/(104) and (006)/(101) obtained by powder X -ray diffraction and the bulk density, each measured with respect to these complex oxides are shown in table 4.
- a SEM photograph ( ⁇ 30,000 magnifications) indicating the primary particles of the complex oxide of Example 5 is shown in FIG. 7, that ( ⁇ 30,000 magnifications) indicating the primary particles of the complex oxide of Example 6 in FIG. 8 and that ( ⁇ 10,000 magnifications) indicating the primary particles of the complex oxide of Example 7 in FIG. 9.
- the scale unit of —line shown in the lower part of the respective photographs indicates 1 ⁇ m.
- the trivarent (Ni+Co) ratio is approximately 100% and the peak intensity ratio of (003)/(104) obtained by the powder X - ray diffraction is lower than 1.2 while that of (006)/(101) is higher than 0.13 and thus the degree of crystallization is exceedingly high. Furthermore, it can be seen from the SEM photographs that the primary particle grow to a great extent and the bulk density became sufficently high in case of the complex oxides of Examples 6 and 7 each subjected to press molding.
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.79 Co 0.165 Al 0 025 (OH) 1 845 (NO 3 ) 0.14 ⁇ 0.2 H 2 O) and suspended in water. Thereafter, boric acid was added to the suspension in an amount such that the molar ration of Ni:Co:Al:B became 790:165:25:20 with respect to the Ni, Co and Al contents in the suspension. To the resultant slurry was added dropwisely a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Al+B) was 1.05. Thereafter, the reaction mixture was spray-dried.
- the obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company) and then pulverized in a mortar to obtain powdery LiNi 0 79 0 Co 0.165 Al 0.025 B 0.020 O 2 .
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.79 Co 0.14 Al 0.05 (OH) 1.86 (NO 3 ) 0.15 ⁇ 0.24H 2 O) and suspended in water. Thereafter, boric acid was added to the suspension in an amount such that the molar ration of Ni:Co:Al:B became 790:140:50:20 with respect to the Ni, Co and Al contents in the suspension. To the resultant slurry was added dropwisely a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Al+B) was 1.05. Thereafter, the reaction mixture was spray - dried.
- the obtained dry gel was put in an alumina boat and heated at 775° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company) , and then pulverized in a mortar to obtain powdery LiNi 0 79 0 Co 0.140 Al 0.050 B 0.020 O 2 .
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.79 Co 0.09 Al 0.10 (OH) 1.92 (NO 3 ) 0.14 ⁇ 0.18 H 2 O) and suspended in water. Thereafter, boric acid was added to the suspension in an amount such that the molar ration of Ni:Co:Al:B became 790:90:100:20 with respect to the Ni, Co and Al contents in the suspension. To the resultant slurry was added dropwisely a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Al+B) was 1.05. Thereafter, the reaction mixture was spray - dried.
- the obtained dry gel was put in an alumina boat and heated at 775° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company) , and then pulverized in a mortar to obtain powdery LiNi 0 79 0 Co 0.090 Al 0.100 B 0 020 O 2 .
- TF-630 type a product of Yamada Electric Company
- reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni 0.8 Co 0.01 Al 0 05 Fe 0 05 (OH) 1 96 NO 3 ) 0.14 ⁇ 0.18 H 2 O) and suspended in water to form a slurry.
- a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Al+Fe) was 1.05. Thereafter, the reaction mixture was spray-dried.
- the obtained dry gel was put in an alumina boat and heated at 725° C.
- the obtained reaction product was filtered, washed with water and suspended in water to form a slurry.
- a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Mn) was 1.05.
- the reaction mixture was spray-dried.
- the obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company), and then pulverized in a mortar to obtain powdery LiNi 0.800 Co 0.150 Mn 0.050 O 2 .
- the chemical composition of the heating product was LiNi 0.80 Co 0.10 Al 0.10 O 2 .
- the chemical composition of the heating product was LiNi 0.79 Co 0.165 Al 0.025 B 0.02 O 2 .
- the trivalent (Ni+Co) ratio and the physical properties such as BET specific surface area, the peak intensity ratios (003)/(104) and (006)/(101) obtained by powder X -ray diffraction, each measured with respect to these complex oxides are shown in table 5.
- a SEM photograph ( ⁇ 1,500 magnifications) indicating the primary particles of the complex oxide of Example 8 is shown in FIG. 14, that ( ⁇ 1,500 magnifications) indicating the primary particles of the complex oxide of Example 10 is shown in FIG. 15 and that ( ⁇ 1,500 magnifications) indicating the primary particles of the complex oxide of Example 11 is shown in FIG. 16.
- the scale unit of—line shown in the lower part of the respective photographs indicates 10 ⁇ m.
- table 6 shows the results of the battery test (charge and discharge test) conducted according to Experimental Example 4 using the respective complex oxides of Examples 5 ⁇ 11 and Comparative Examples 4 ⁇ 5 to evaluate initial discharge capacity (mAh/g), discharge capacity at 100th cycle (mAh/g) and decrease rate of discharge capacity at 100th cycle (%).
- Example 5 (mAh/g) (mAh/g) (%) Example 5 173 161 7.2
- Example 6 176 165 6.4
- Example 7 176 165 6.0
- Example 8 185 177 4.3
- Example 9 186 180 3.2
- Example 10 176 169 4.2
- Example 11 159 147 7.6 Comparative 148 111 24.7
- Example 4 Comparative 139 98 29.6
- Example 5
- the lithium nickel cobalt complex oxides have a tendency to decrease the initial discharge capacity with the increase in the Al content therein and correspondingly with decrease in the Co content as compared with the complex oxide of the Comparative Example 3 shown in table 3, and that the improvement in the cycle characteristics may be achieved by the addition of boron. Furthermore, it is understood that the addition of Fe shows a great tendency to decrease the initial discharge capacity as compared with the case of Al addition. However, the complex oxide of the present invention is superior in the initial capacity and the cycle characteristics to those of the Comparative Examples 4 and 5.
- the lithium nickel cobalt complex oxide of the present invention especially one doped completely with Al and/or B as the solid liquid is satisfactory secondary battery positive electrode material as the battery performance.
- D h k l (angstrom) represents size of crystallite in vertical direction to the face (hkl), A (angstrom) the wave length of X-ray, G (rad) the width of diffraction pattern, ⁇ (° ) angle of diffraction, and k a constant.
- the trivalent (Ni+Co) ratio is value expressed in percentage the ratio of the trivalent (Ni+Co) to the total (Ni+Co), and is measured by oxidation-reduction titration. 0.2 Gram of a sample was dissolved in 0.25 M FeSO 4 -3.6 N H 2 SO 4 solution, and 2 ml of a concentrated phosphoric acid was added to the solution. The mixture was titrated with a 0.1 N KMnO 4 solution. Blank test was carried out in the same manner as in the above. The trivalent (Ni+Co) % was calculated by the following equation.
- f represents the factor of the 0.1 N KMnO 4 solution
- X 0 the titer of the blank test (ml)
- X the titer of the sample (ml)
- m the amount of the sample (g)
- A the content of Ni (%)
- B the content of Co (%)
- the trivalent (Ni+Co) ratio (%) in the sample 10f ( X 0 ⁇ X)/m (A/5.871+B/5.893)
- the sample was degassed by heating under the flow of a mixed gas of 30% nitrogen and, 70% helium, and thereafter specific surface area was measured according to the BET one point continuous flowing method using “MONOSORB” (a product of Yuasa Ionics Co., Ltd.).
- the lithium nickel complex oxide, acetylene black as a conductive agent and tetrafluoroethylene as a binder were mixed in a ratio of 88:6.0:6.0% by weight. Thereafter, the mixture was subjected to compression molding on stainless steel mesh, thereby obtaining pellets each having a diammeter of 18 mm. The resultant pellets were dried at 200° C. for 2 hours, and used as a positive electrode material.
- a negative electrode material As a negative electrode material was used a rolled lithium metal sheet pressed-bonded to a stainless substrate. As a diaphragm, porous membrane made of polypropylene (“Cell Guard 2502”) and a glass filter-paper filter were used. There was used an electrolyte in which 1 M LiClO 4 was dissolved in an ethylene carbonate/dimethylmeth oxyethane mixture (1:1 weight ratio). The procedures up to completion from setup of a test cell (semi-open type cell) were conducted in an argon replaced dry box. The charging and discharging for this lithium battery were performed under a voltage control between 3.0 V and 4.3 V at a constant current density of 0.4 mA/ cm 2 .
- a cell was prepared by a similar manner as in Experimantal Example 3 and charging was conducted under the constant current density of 0.4 mA/cm 3 until it reached 4.4 V. After the completion of charging, the cell was decomposed to take out the positive electrode. The positive electrode was washed with the electrolyte solution and dried under vacuum. The dried positive electrode was subjected to a differential thermal-analysis apparatus under flow of nitrogen at a heating rate of 2° C./min. to examine the exothermic peak temperature at which oxygen evolution occurs.
Abstract
Description
- The present invention relates to a lithium nickel cobalt complex oxide having a high purity, a high crystallinity, a high battery capacity and stable structure so that the degree of decrease in the capacity is little even with increasing the number of charging and discharging cycle, to a process for preparing the same, and to a positive electrode active material for a secondary battery.
- As electronic appliances have been rendered small and portable in recent years, there has been increased a demand for a lithium ion secondary battery having a light weight and a high energy density in place of nickel/cadmium battery and nickel hydrogen battery.
- As active materials of positive electrode for this lithium ion secondary battery, there are known LiNiO2 and LiCoO2 which are layered compounds capable of intercalating and deintercalating lithium ion. Of them, LiNiO2 is being expected owing to its higher electric capacity than LiCoO2.
- However, LiNiO2 has not yet been put to practical use because it has problems in the charging and discharging cycle characteristics, the storage stability and the stability at a high temperature . Only LiCoO2 has been practically used as the positive electrode active material.
- Although various attempts have been made to improve the above faults of LiNiO2 for its utilization as the positive electrode active material for a secondary battery, there has not yet been realized one wherein all of the above faults have been solved.
- That is, in case of LiNiO2 it is known that when much lithium ions are liberated therefrom (during charge), the structure becomes unstable owing to the two dimention structure and therefore the cycle property, storage stability and high temperature stability of the lithium ion secondary battery are bad [for example, see J. Electrochem. Soc., 140 [7]p. 1862-1870 (1993), Solid State Ionics, 69 p. 265-270 (1994)]. Although many attempts have been made to stabilize the structure by replacing a part of Ni by other components (Co, Mn, Fe, Ti, V etc.) for the purpose of securing the structure stability with elimination of the above faults, it was difficult to obtain highly purified and completely doped crystals as a solid solution on an industrial scale because there have been practically applied dry blending and heating processes.
- Also, an attempt has been made to control to certain specific level the physical properties such as shape and size of LiNiO2 particles and its doped product with other components as solid solution. However, the satisfactory results could not be achieved. For example, Japanese Patent Laid-open No. 151998/1993 proposes an improvement wherein the particle size distribution is specified to such extent that 10% cumulative size is 3˜15 μm, 50% cumulative size 8˜35 μm and 90%
cumulative size 30˜80 μm, However, it is very difficult to adjust the particle size distribution to such extent by grinding the positive electrode active material and this is not practical process. - Usually, LiNiO2 has been prepared by mixing lithium components (LiOH, Li2CO3, LiNO3 etc.) with nickel components (hydroxide, carbonate etc.) in a dry state and thereafter subjecting the mixture to the reaction, and hence the heating at an elevated temperature for a long time was required. Consequently, the crystal growth proceeds but some of lithium is evaporated off and NiO as a by-product is formed, thereby the lowering of the purity is caused.
- Therefore, it was difficult to prepare highly purified product by the dry process in case that the primary particle size is small. On the other hand, in case that the primary particle size is large, a considerable lattice defect in the structure is caused and results in lowering of the purity. It was impossible to adjust crystal size to a desired, with keeping crystallinity and purity at high level by the dry process.
- An object of the present invention is to provide a novel lithium nickel cobalt complex oxide which has improved properties with respect to the above faults of the hitherto known LiNiO2 and its related complex oxide, namely which has a high purity, a high crystallinity, a high battery capacity and stable structure so that the degree of decrease in the capacity is little even by increasing the number of charging and discharging cycle.
- Another object of the present invention is to provide a process for preparing said lithium nickel cobalt complex i oxide by a process via wet process which is different from the hitherto known dry process whereby the size of the formed spherical and secondary and primary particle may be set to a desired.
- A further other object of the present invention is to provide a positive electrode active material for a lithium ion secondary battery containing as an effective component said lithium nickel cobalt complex oxide.
- As a result of having studied ardently to achieve the above objects, the present inventors have found that a complex oxide which may be represented by the following general formula (I) and which may be prepared at the first time by a process via wet process described later coincides with the above objects;
- LiyNi1-xCox1Mx 2O2 (I)
- (wherein M represents at least one element selected from the group consisting of Al, Fe, Mn and B, y represents 0.9≦y≦1.3, x1+x2=x, x represents 0<x≦0.5, x1 represents 0<x1<0.5; when M is at least one element among Al, Fe and Mn, x2 represents 0<x2<0.3, when M is B, X2 represents 0<x2<0.1 and when M is a combination of B and at least one element among Al, Fe and Mn, x2 represents 0<x2<0.3 wherein the proportion of B is a range of from 0 to 0.1.
- The novel complex oxide of the present invention has the following features.
- The first feature lies in the composition represented by the above general formula (I) based on which with holding as high battery capacity as LiNiO2, not only its faults i.e. cycle property (deterioration of discharge capacity caused by increasing the number of cycle) and high temperature stability may be improved but also the amount used of an expensive cobalt may be suppressed to the minimum thereby economical merit may be realized.
- The second feature of the complex oxide lies in that it has a high crystallinity and a high purity as identified by its X -ray diffraction pattern. That is, it is highly purified complex oxide to such extent that X- ray diffraction pattern shows that a ratio in the peak intensity of the face (003) to the face (104) i.e., (003) /(104) is 1.2 or higher and a ratio in the peak intensity of the face (006) to the face (101) i.e., (006)/(101) is 0.13 or lower, said face being defined by Miller indices hkl, the proportion of (Ni3→+Co3.) to the total (Ni +Co) being 99% by weight or higher, a BET specific surface area being 0.1˜2 m2/g, an average secondary particle size D being in the range of 5˜100 μm with 10% of the particle size distribution being 0.5 D or higher and 90% 2 D or lower, the surface of the spherical secondary particle being uneven as observed with a scanning electron microscope (SEM) and the primary particle constituting the spherical secondary particle being in the range of 0.2˜30 μm in terms of long diameter with the average diamter of 0.3˜30 μm as observed with a SEM.
- In case of LiNiO2 and its related complex oxide, when a part of the Ni is intended to be doped with other component(s) as the solid solution it is difficult to dope them homogeneously by the hitherto known dry process because the homogeneity is lowered in proportion to the amount added of other component(s) whereby not only the battery capacity is lowered but also the improvement in the cycle property, the heat resistance and the electrolytic solution resistance are insufficient.
- The lithium nickel cobalt complex oxide of the present invention can be kept in high purity, in spite of being one doped with at least one element selected from the group of consisting of Al, Fe, Mn and B. As shown in Examples described later, the interlayer distance may be efficiently shortened especially by using Co together with Al and /or B whereby the structural instability of Ni by reversible deintercalation of lithium ion can be avoided. The greatest feature of the present invention is that Co and at least one element selected from the group of consisting of Al, Fe, Mn and B may be doped as solid solution in a small amount and uniformly into the lithium nickel complex oxide. Such lithium nickel cobalt complex oxide of the present invention can be obtained as the composition having a high purity and a high crystallinity by the wet process as described later.
- The third feature of the complex oxide of the present invention is that there can be obtained uniform and primary particle and that shape and size of the secondary paricle may be adjusted to the desired.
- When an attention is paid to the size of the primary particle, in general the size of the primary particle is important for a layered compound represented by LiMO2 in the light of the reversible deintercalation of lithinm ion. Finer the primary particle, better ionic conductivity in the inside of the solid and lithium ion is more reversibly deintercalatable with the outside.
- On the other hand, in considering the complex oxide from an aspect of the crystallization degree when the crystallization degree is small the crystal growth does not proceed sufficiently and the purity becomes low inevitably. Also, in case that the primary particle is small the storage stability is poor owing to moisture absorpbility and so good battery characteristics can not be achieved stably. Moreover, it is desirable that the primary particle is large taking the high temperature resistance and the reactivity with the electrolytic solution into consideration. As a result of having studied ardently, the present inventors have succeeded in the preparation of the complex oxide having an uniform primary particles of such that a long diameter of the primary particles is in the range of 0.2˜30 μm, preferably 1˜20 μm by combined wet process-spray (or freeze) drying process-press molding and heating processes as described later.
- A complex oxide wherein both the primary and secondary particles are uniform may be prepared by employing especially spray drying-heating processes. A long diameter of the primary particles is in the range of 0.2˜30 μm, preferably 1˜20 μm and its average size is in the range of 0.3˜30 μm when observed with a SEM. An average size D of the spherical secondary particle formed by spray drying-heating processes is in the range of 5˜300 μm, preferably 5˜100 μm, more preferably 5˜20 μm and the particle is uniform to such extent that 10% of the particle size distribution is 0.5 D or higher and 90% 2D or lower, and the surface of the spherical secondary particle is uneven as can be seen under observation of a SEM.
- Also, the particle ratio (a ratio of the long diameter to the short diameter) of the spherical secondary particles when observed with a SEM lies in the range of a maximum of 1.5 or less and an average of 1.2 or less with 90% or more of them being distributed in 1.3 or less, indicating that they are uniform particles even when there was included some particles having slightly larger particle ratio than defined above in the complex oxide prepared by pulverization after the heating.
- It is understood from such physical properties that not only the spherical product of the present invention, preferably one prepared by the spray drying-heating processws is suitable for the closest packing density but also they have advantages when used as battery that the contact surface with each of an electrolyte and a conductive agent becomes large so that it is easy to reversibly deintercalate Li ions with the outside.
- The size of the spherical secondary particles can be set to the range of from 5 μm to 100 μm as desired. However, an average size of about 5˜30 μm is desirable for use as the battery material from the viewpoint of processibility. Also, the BET specific surface area lies in the range of 0.1˜2 m2/g. When it was used as the battery material, since there is no increase in the viscosity of an electrolyte the lowering in conductivity is not caused.
- Also, for the purpose of setting the average long diameter of the primary particle to the range of about 1 μm ˜30 μm it may be more simply and conveniently achieved by subjecting the spray (or freeze) dried product as above-mentioned to press molding. In case that the primary particle is large, it has physical properties that the purity and the crystallinity are high and that the high temperature stability is excellent, and therefore it may be preferably used as the positive electrode active material for a secondary battery which would be used under a severe condition. The bulk density becomes large due to press molding applied. That bulk density is high is plus for elevation of the battery capacity.
- The following illustrates a process for preparing the complex oxide of the present invention which is represened by the above general formula (I) in details.
- In preparing the complex oxide represened by the above general formula (I), the following processes are applied according to the three kinds of classifications that {circle over (1)} M is at least one element of Al, Fe and Mn, {circle over (2)} M is B and {circle over (3)} M is the combination of B and at least one element of Al, Fe and Mn.
- That is, {circle over (1)} in a process for preparing a complex oxide represented by the general formula (I)
- LiyNi1-xCox1Mx2O2 (I)
- (wherein M is at least one element selected from the group consisting of Al, Fe and Mn), said complex oxide may be prepared by adding-an amount of a lithium compound corresponding to the number of atomic moles of Li indicated by y to a basic metal salt represented by the general formula (II)
- Ni1-xCox1Mx2(OH)2 (1-x+x1)-3x2−n, (An),·mH2O (II)
- [wherein M represents at least one element selected from the group consisting of Al, Fe and Mn, x represents 0<x≦ 0.5, x, is 0<x1<0.5, x2 represents 0<x2≦ 0.3, x1+x2=x, An- represents an anion having a valence of n (n=1˜3) and z and m are positive numbers respectively satisfying the ranges of 0.03≦z ≦0.3, 0≦m<2] in an aqueous medium to form a slurry, spray or freeze drying the formed slurry and heating the spray or freeze dried product at a temperature of about 600° C.˜ 900° C. for 4 hours or more in an oxidative atmosphere.
- {circle over (2)} In a process for preparing a complex oxide represented by the general formula (I)
- LiyNi1-xCox1Mx 2 O2 (I)
- (wherein M represents B), said complex oxide may be prepared by adding a boron compound containing X2 mol % of boron [x 2 represents 0<x2<0.1, the relationship among x, x1 and x2 is expressed by x2=x−x1] to a basic metal salt represented by the general formula (III)
- Ni1-xCox1(OH)2 (1-x+x1)-nz (An-) z·mH2O (III)
- [wherein x represents 0<x≦0.5, x, represents 0<x121 0.5, An- represents an anion having a valence of n ( n=1˜3) and z and m represent positive numbers respectively satisfying the ranges of 0.03≦z≦0.3, 0 ≦m<2] in an aqueous medium, subsequently adding thereto an amount of a lithium compound corresponding to the number of atomic moles of Li indicated by y to form a slurry, spray or freeze drying the formed slurry and heating the spray or freeze dried product at a temperature of about 600° C.˜900° C. for 4 hours or more in an oxidative atmosphere.
- {circle over (3)} In a process for preparing a complex oxide represented by the general formula (I)
- LiyNi1-xCox1Mx 2O2 (I)
- (wherein M represents the combination of B and at least one element of Al, Fe and Mn), said complex oxide may be prepared by adding a boron compound containing x4 mol % of boron [x4 represents 0<x4<0.1, the relationship among x4, x3 and x2 is expressed by x4+x3=x2] and an amount of a lithium compound corresponding to the number of atomic moles of Li indicated by y to a basic metal salt represented by the general formula (IV)
- Ni1-xCox1Nx3(OH)2 (1-x+x1)÷3x3−n z (An-)z·mH2O (IV)
- [wherein N represents at least one element of Al, Fe and Mn, in this case M in the general formula (I) contains both the N and B, and if the content of B therein is indicated by x4, x represents 0<x≦0.5, x1 represents 0<x1<0.5, x3 represents 0<x3≦0.3−x4, x1+x3+x4=x, An- represents an anion having a valence of n ( n=1˜3), and z and m represent positive numbers respectively satisfying the ranges of 0.03≦z≦0.3, 0≦m<2] in an aqueous medium, to form a slurry, spray or freeze drying the formed slurry and heating the spray or freeze dried product at a temperature of about 600° C.˜900° C. for 4 hours or more in an oxidative atmosphere.
- As the water soluble lithium compound and the basic metal salt which may be represented by the general formulae (II) , (III) or (IV) (hereinafter, referred to as “the basic metal salt” collectively), there may be employed one each containing an anion which is evaporated off during the heating.
- As the examples of the lithium compound, there may be selected one or more from among LiOH, LiNO3 Li2CO3 and hydrates thereof.
- As the examples of the boron compound, boric acid and lithium tetraboric acid may be preferably employed.
- As the example of An- in the basic metal salt there may be selected from among the anions shown by NO3, Cl , Br-, CH3COO-, CO3 2- and SO4 2-.
- In these compounds, LiOH as the lithium compound, boric acid as the boron compound and a basic metal salt wherein an anion is nitrate ion are used from the viewpoint of yield, reactivity, effective utilization of the resources and oxidation accelerating effect. The combination of these 3 kinds of compounds is particularly preferred from the viewpoint of battery characteritics.
- As the basic metal salt which may be employed in the present invention, is preferable the basic salt having a specific composition that size of the primary particle is as fine as below 0.1 μm when measured by the Scherrer's method.
- Also, it is preferred that this fine particle has a BET specific surface area of 10 m2/g or higher, preferably 40 m2/g or higher, more preferably 100 m2/g or higher. As to the BET specific surface area, if it is measured after the basic metal salt in an aqueous solution has been dried, as the very fine primary particles aggregates during dry process, then BET specific surface area of the aggregate is measured. If aggregation power is strong, nitrogen gas cannot enter into it and the value of BET specific surface area becomes small. Accordingly the basic metal salt which is practically reacted with a lithium compound in aqueous solution shows a high BET specific surface area so that the surface is highly reactive. However, BET specific surface area was set to 10 m2/g or higher from the above actual circumstances. The basic metal salt having such specific composition has a layered structure, and the chemical composition and the crystal structure where M is at least one of Al, Fe and Mn are similar to those of hydroxide of Ni 1-xCox1Mx2. The chemical composition and the crystal structure where M is B are similar to those of hydroxide of Ni1-xCox 1. And the chemical composition and the crystal structure where M is the combination of B and at least one of Al, Fe and Mn are similar to those of hydroxide of Ni1Cox1Nix3. Moreover, in all cases, the basic metal salt is microcrystalline whose surface is highly active. When it is reacted with a lithium compound such as LiOH, an extremely desirable precursor of LiyNi1-xCox1Mx2O2 is formed.
- Highly purified LiyNi1-xCox1M2O2 having an extremely high crystallinity at which the present invention aims can be obtained only when the basic metal salt having such a specific composition is used. The hydroxides in the above is inferior in the reactivity with the lithium compound to the basic metal salt. On the other hand, when the amount of an anion in the basic metal salt is increased, the basic metal salt is deviated from the layered structure, and the anion acts inhibitively on the formation of Li ,Ni1 xCox1Mx2 O 2 during the heating, thereby the desired compound having a high purity and an extremely high crystallization degree cannot be obtained.
- The basic metal salt to be used in the present invention can be prepared by adding an amount of about 0.7 ˜0.95 equivalent, preferably about 0.8˜0.95 equivalent of an alkali based on Ni1-xCox1Nx3 salt, Ni1 x Cox1 salt or Ni1-xCox1Nx3 salt under the condition below about 80° C. to effect the reaction. Examples of the alkali to be used in the reaction include alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, amines and the like. In this connection, it is preferable that this basic metal salt is matured at 20˜70° C. for 0.1˜10 hours after its preparation. Subsequently, any by-products are removed by washing with water and the lithium compound is added, and the boron compound is further added for the purpose of preparing a complex oxide containing B.
- For drying the slurry obtained by such a reaction, spray or freeze drying method is desirable. The spray drying method where drying can be instantaneously accomplished and the spherical particles can be obtained is preferred from the viewpoint of the spherical granulation nature and the uniformity of the composition (in dry process requiring some drying time, lithium migrates into the surface of particles to give a non-uniform composition).
- The heating is effected at a temperature of 600° C.˜ 800° C., preferably 700° C.˜750° C. for 4 hours or higher, preferably about 4 - 72 hours, more preferably about 4˜ 20 hours under an oxidative atmosphere (under the flow of oxygen). If the heating time is 72 hours or, more, not only it makes cost up but also it causes evaporation of Li thereby the proportion of trivalent (Ni+Co) to the total (Ni+Co) becomes rather low and the purity becomes bad.
- In the known technique by the drying process regarding the heating, the heating of at least 20 hours was required for Ni which is hard to convert into trivalent from divalent. In the light of the fact, the process of the present invention which may be carried out even at shorter heating time than 20 hours is very economical and advantageous.
- The second process is press molding process which is advantageous for the purpose of making the primary particle large and further making the bulk density high.
- The dry product obtained by the spray drying or freeze drying process above-mentioned is press molded and then heated, whereby not only the size of the primary particle may be optionally set within the range of 1 - 30 μm, but also there can be obtained the complex oxide having high bulk density, degree of crystallization and purity.
- The spherical particle that is the spray dried product is excellent powder with respect to flowability, molding and filling properties, and is a good material to be pressed into a shape as it is according to the conventional manner.
- Although the pressure for molding may be varied depending on the pressing machine to be applied and the amount to be fed and is not limited particularly, usually about 500˜3,000 kg/cm2 is suitable.
- Pressing machine to be applied is not limited particularly and it may be one capable of pressing. However, tablet compressing machine, briquette, roller compactor may be suitably employed.
- The density of the press molded product may be about 1 ˜4g/cc, preferably about 2˜3g/cc.
- The press molding is very useful in that moving distance among molecules becomes short and crystal growth during the heating is accelerated. Accordingly, it is not always necessary that the material to be subjected to the press molding is spray dried spherical particle product. The freeze dried product may also be used.
- This press molded product can be heated as it is. The heating is effected at a temperature of usually 600˜900° C. , preferably 700° C.˜800° C. for a period of 4 hours or higher, preferably 10˜72 hours under an atmosphere of oxygen.
- The longer the heating time, the larger the size of the primary particle. Therefore, the heating time is determined depending on the desired size of the primary particle.
- For accomplishing the heating in a short time, 2 times heating of pre-heating and after-heating may be applied. The slurry obtained by the process described previously is spray- or freeze-dried and the spray- or freeze-dried product is first pre-heated at a temperature of about 600° C. ˜900° C. for 0.5 hour or more (preferably 0.5˜4 hours) under an oxidative atmosphere, the obtained pre-heating product is pulverized if necessary and pressed into a shape, and then after-heated at a temperature of about 600° C.˜ 900° C. for 1 hour or more (preferably 4˜48 hours) under an oxidative atmosphere, The total time requird for the heating may be shortened by employing this process.
- The thus obtained complex oxide of the present invention which may be represented by the general formula ( I) retains high battery capacity of 160˜180 mAh/g even after 100 charging and discharging cycles and has an improved high temperature cycle property (stability) as is apparent from the Examples described later, and hence it may be effectively utilized as a positive electrode active material for a secondary battery.
- FIG. 1 is powder X -ray diffraction patterns of the complex oxides obtained in Examples 1˜4 and Comparative Examples 1˜2, respectively.
- FIG. 2 is SEM photograph (×1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 1.
- FIG. 3 is SEM photograph (×1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 4.
- FIG. 4 is powder X -ray diffraction pattern of the complex oxide obtained in Example 5.
- FIG. 5 is powder X - ray diffraction pattern of the complex oxide obtained in Example 6.
- FIG. 6 is powder X -ray diffraction pattern of the complex oxide obtained in Example 7.
- FIG. 7 is SEM photogragh (×30,000) of the complex oxide obtained in Example 5.
- FIG. 8 is SEM photograph (×3,000 magnifications) indicating the primary particles of the complex oxide obtained in Example 6.
- FIG. 9 is SEM photograph (×10,000 magnifications) indicating the primary particles of the complex oxide obtained in Example 7.
- FIG. 10 is powder X -ray diffraction pattern of the complex oxide obtained in Example 8.
- FIG. 11 is powder X -ray diffraction pattern of the complex oxide obtained in Example 9.
- FIG. 12 is powder X -ray diffraction pattern of the complex oxide obtained in Example 10.
- FIG. 13 is powder X -ray diffraction pattern of the complex oxide obtained in Example 11.
- FIG. 14 is SEM photograph (×1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 8.
- FIG. 15 is SEM photograph (×1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 10.
- FIG. 16 is SEM photograph (×1,500 magnifications) indicating the primary particles of the complex oxide obtained in Example 11.
- The present invention is more specifically illustrated by the following examples.
- There was prepared a mixed aqueous solution of 2.0 M nickel nitrate and cobalt nitrate wherein the molar ratio of Ni:Co was 80:19. This mixed aqueous solution and 1.0 M aqueous sodium hydroxide solution were added to a reaction vessel under stirring using quantitative pumps while the amount added of aqueous sodium hydroxide solution was adjusted so as to maintain pH 8.0 at a reaction temperature of 25° C., thereby the continuous reaction was carried out. The residence time of average 10 minutes was taken.
- The reaction product overflowed from the reaction vessel during the continuous reaction was collected in the receiver tanc. The reaction was completed when the necessary amount of the reaction product was collected.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0. 8Co0 19 (OH)1 833 (NO3) 0 147·0.16 H2O) and suspended in water. And then, boric acid was added to the suspension in an amount such that the molar ratio of Ni:Co:B became 80:19:1 with respect to the Ni and Co contents in the suspention. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni +Co+B) became 1.05.
- Thereafter, the reaction mixture was spray-dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company)
- The chemical composition of the heating product was LiNi0. 80Co0.19B0.01O2.
- There was prepared a mixed aqueous solution of 2.0 M nickel nitrate and cobalt nitrate wherein the molar ratio of Ni:Co was 80:19.5. This mixed aqueous solution and 1.0 M aqueous sodium hydroxide solution were simultaneously added so as to maintain pH 8.0 according to similar manner as in Example 1, whereupon the continuous reaction was conducted at 25° C. for 10 minutes of the resident time.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.8Co0.195(OH)1.86 (NO3)0.130· 0. 22 H2O) and suspended in water. And then, boric acid was added to the suspension in such amount that the molar ratio of Ni:Co:B became 80:19.5:0.5 with respect to the Ni and Co contents in the suspension. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni +Co+B) became 1.05. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- The chemical composition of the heating product was LiNi0. 80Co0. 195B0. 005 O2.
- There was prepared a mixed aqueous solution of 2.0 M nickel nitrate and cobalt nitrate wherein the molar ratio of Ni:Co was 80:18. This mixed aqueous solution and 1.0 M aqueous sodium hydroxide solution were simultaneously added so as to maintain pH 8.0 according to similar manner as in Example 1, whereupon the continuous reaction was conducted at 25° C. for 10 minutes of the resident time.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.8Co0.18(OH)1.79(NO3)0.17·0.3 H2O) and suspended in water. And then, boric acid was added to the suspension in such amount that the molar ratio of Ni Co:B became 80:18:2 with respect to the Ni and Co contents in the suspension. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni+Co|B) became 1.05. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- The chemical composition of the heating product was LiNi0.80Co0.18B0.02O2.
- There was prepared a mixed aqueous solution of 2.0 M nickel nitrate and cobalt nitrate wherein the molar ratio of Ni:Co was 80:15. This mixed aqueous solution and 1.0 M aqueous sodium hydroxide solution were simultaneously added so as to maintain pH 8.0 according to similar manner as in Example 1, whereupon the continuous reaction was conducted at 25° C. for 10 minutes of the resident time.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.8Co0.15(OH)1.76(NO3)0.14·0.25 H2O) and suspended in water. And then, boric acid was added to the suspension in such amount that the molar ratio of Ni Co:B became 80:15:5 with respect to the Ni and Co contents in the suspension. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni+Co+B) became 1.05. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- The chemical composition of the heating product was LiNi0.80Co0.15B0.05O2.
- There was prepared a mixed aqueous solution of 2.0 M nickel nitrate and cobalt nitrate wherein the molar ratio of Ni:Co was 80:10. This mixed aqueous solution and 1.0 M aqueous sodium hydroxide solution were simultaneously added so as to maintain pH 8.0 according to similar manner as in Example 1, whereupon the continuous reaction was conducted at 25° C. for 10 minutes of the resident time.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.8Co0.01(OH)1.68(NO3)0.12·0.19 H2O) and suspended in water. And then, boric acid was added to the suspension in such amount that the molar ratio of Ni Co:B became 80:10:10 with respect to the Ni and Co contents in the suspension. To the resultant slurry 3.0 M aqueous lithium hydroxide solution was added dropwisely in an amount such that the molar ratio of Li/(Ni+Co+B) became 1.05. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- The chemical composition of the heating product was LiNi0.80Co0.10B0.10O2.
- There was prepared a mixed aqueous solution of 2.0 M nickel nitrate and cobalt nitrate wherein the molar ratio of Ni:Co was 80:20. This mixed aqueous solution and 1.0 M aqueous sodium hydroxide solution were simultaneously added so as to maintain pH 8.0 according to similar manner as in Example 1, whereupon the continuous reaction was conducted at 25° C. for 10 minutes of the resident time.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.. 8Co0.2(OH)1.87 (NO3)0 13·0.14 H2O) and suspended in water. And then, 3.0 M aqueous lithium hydroxide solution was added dropwisely to the suspension in an amount such that the molar ratio of Li/(Ni+Co) became 1.05. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company).
- The chemical composition of the firing product was LiNi0.80Co0.20O2.
- 1.00 Mol lithium hydroxide, 0.80 mol nickel hydroxide, 0.19 mol cobalt hydroxide and 0.01 mol boric acid were sufficiently mixed in dry state and pulverized in a mortar, and then pelletized into size of 14 mm of a diameter x 2 mm of a thickness. The resultant pellets were heated at 750° C. for 48 hours in an atmosphere of oxygen.
- The chemical composition of the heat-treated product was LiNi0.80Co0.19B0.01O2.
- The respective powder X - ray diffraction patterns of the complex oxides obtained Examples 1˜4 and Comparative Examples 1˜2 are shown in FIG. 1. As is apparent from FIG. 1, any peak based on by-product was not recognized in each process and the complex oxides are estimated to have uniformly doped layered structure.
- The respective SEM photographs (×1,500 magnifications) indicating the primary particles of the complex oxides obtained in Examples 1 and 4 are shown in FIGS. 2 and 3. The scale unit of—line shown in the lower part of the respective photographs indicates 10 μm.
- Also, the respective crystalline sizes estimated from the X - ray diffraction measured with respect to the basic metal salts obtained by the continuous reaction in Examples 1˜4 stated above and Examples 5˜12 described later are summarized in table 1. It can be seen from table 1 that the crystalline size is below 0.1 μ in all cases, indicating that there was formed the basic metal salt having fine primary particle.
TABLE 1 Crystalline Size of Basic Metal Salt Obtained by the Continuous Reaction No. Crystalline Size (angstrom) Example 1 38.1 Example 2 42.5 Example 3 34.6 Example 4 45.1 Example 5 37.9 Example 6 46.2 Example 7 37.4 Example 8 38.1 Example 9 35.3 Example 10 40.5 Example 11 43.5 Example 12 41.4 - Furthermore, the ratio of the trivalence in (Ni+Co) and the physical properties such as BET specific surface area, the peak intensity ratios (003)/(104) and (006)/(101) estimated by powder X -ray diffraction, an average secondary particle size measured by laser microtrack and long diameter of the primary particle obtained from observation of the SEM photograph, each measured with respect to these complex oxides are shown in table 2.
- The trivalent (Ni+Co) ratio and the BET specific surface area were measured according to Experimental Examples 2 and 3, respectively.
TABLE 2 Average Ratio Average Long of the Second- Diameter Trivalence Ratio Ratio ary of in of of Particle Primary (Ni + Co) BET (003)/ (006)/ Size Particle No. (%) m2/g (104) (101) (μm) (μm) Example 1 99.8 0.1 1.310 0.101 15.21 0.72 Example 2 99.7 0.2 1.304 0.102 17.21 0.65 Example 3 99.9 0.1 1.273 0.111 18.01 0.62 Example 4 99.1 0.1 1.211 0.106 16.42 0.68 Comparative 89.5 0.2 0.873 0.268 17.21 0.61 Example 1 Comparative 99.6 0.1 1.245 0.104 18.21 0.67 Example 2 - From the results shown in table 2, in case that M in the general formula (I) is B, the complex oxide of Comparative Example 1 wherein the amount added (content) of B is 10 mol % has low trivalent ratio. The peak intensity ratio of (003)/(104) obtained by the powderX -ray diffraction is lower than 1.2 while that of (006)/(101) is higher than 0.13 and thus the crystallinity is low. For these facts, in case that M in the general formula (I) is B. it is more preferable that the numerical value of x2 is 0<x2≦0.05.
- With respect to other physical properties, the complex oxides in the above Examples and Comparative Examples 1˜2 have the similar physical properties each other because all of them were prepared by wet-spray drying process.
- Moreover, table 3 shows the results of the battery test (charge and discharge test) conducted according to Experimental Example 4 using the respective complex oxides of Examples 1˜4 and Comparative Examples 1˜2 to evaluate initial discharge capacity (mAh/g), discharge capacity at 100th cycle (mAh/g) and decrease rate of discharge capacity at 100th cycle (%). In comparison with the complex oxide of Comparative Example 3 prepared by dry process, the complex oxides of Examples 1˜4 were recognized to have the improved cycle characteristics and initial discharge capacity.
TABLE 3 Initial Decrease Rate of Discharge Discharge Capacity Discharge Capacity Capacity at 100th Cycle at 100th Cycle No. (mAh/g) (mAh/g) (%) Example 1 187 182 2.7 Example 2 185 174 5.9 Example 3 184 178 3.3 Example 4 178 167 6.2 Comparative 152 89 41.4 Example 1 Comparative 184 171 9.3 Example 2 Comparative 163 112 31.2 Example 3 - It can be seen from table 3 that the complex oxides of Examples 1˜4, each containing boron have improved cycle characteristics in comparison with the complex oxide of Comparative Example 2 containing no boron, and especially the comlex oxides of Examples 1˜3 wherein the content of boron is in the range of 0.05˜2 mol% have further improved initial discharge capacity.
- There was prepared a mixed aqueous solution of 2.0 mol/l nickel nitrate, cobalt nitrate and aluminum nitrate wherein the molar ratio of Ni:Co:Al was 8:1:1. This mixed aqueous solution and 1.0 mol/l aqueous sodium hydroxide solution were continuously added under the condition of the reaction pH of 8.0, the reaction temperature of 25° C. and vigorous stirring.
- The obtained reaction mixture was filtered, washed with water and suspended in water thereby obtaining a Ni0 80Co 0.10Al0.10(OH)1.7(NO3)0.40 slurry. A 3.0 mol/l aqueous lithium hydroxide solution was added dropwisely to the obtained slurry in an amount such that the atomic ratio of Li/(Ni+Co+Al) was 1.05 with respect to the (Ni+ Co+Al) content in the above slurry to effect reaction. Thereafter, the reaction mixture was spray dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace, and pulverized in a mortar to obtain powdery LiNi 0. 797Co0.101Al0.102O2.
- There was prepared a mixed aqueous solution of 2.0 mol/l nickel nitrate, cobalt nitrate and aluminum nitrate wherein the molar ratio of Ni:Co:Al was 16:3:1. This mixed aqueous solution and 1.0 mol/l aqueous sodium hydroxide solution were continuously added under the condition of the reaction pH of 8.0, the reaction temperature of 25° C. and vigorous stirring.
- The obtained reaction mixture was filtered, washed with water and suspended in water thereby obtaining a Ni0 80Co 0.15Al0.05(OH)1.7(NO3)0.35 slurry. A 3.0 mol/l aqueous lithium hydroxide solution was added dropwisely to the obtained slurry in an amount such that the atomic ratio of Li/(Ni+Co+Al) was 1.05 with respect to the (Ni+ Co+Al) content in the above slurry to effect reaction. Thereafter, the reaction mixture was spray dried. The obtained dry gel was pressed into a pellet having ø14 and a thickness of 2 mm under pressure of 2 t/cm2 using a static compressor. The pellet was put in an alumina boat and heated at 750° C. for 48 hours in an atmosphere of oxygen in a tube furnace, and pulverized in a mortar to obtain powdery LiNi 0.785Co0.151Al0.054O2.
- There was prepared a mixed aqueous solution of 2.0 mol/l nickel nitrate, cobalt nitrate and aluminum nitrate wherein the molar ratio of Ni:Co:Al was 16:3:1. This mixed aqueous solution and 1.0 mol/l aqueous sodium hydroxide solution were continuously added under the condition of the reaction pH of 8.0, the reaction temperature of 25° C. and vigorous stirring.
- The obtained reaction mixture was filtered, washed with water and suspended in water thereby obtaining a Ni0 80Co 0.15Al0.05(OH)1.7(NO3)0.35 slurry. A 3.0 mol/l aqueous lithium hydroxide solution was added dropwisely to the obtained slurry in an amount such that the atomic ratio of Li/(Ni+Co+Al) was 1.05 with respect to the (Ni+ Co+Al) content in the above slurry to effect reaction. Thereafter, the reaction mixture was freeze dried. The obtained dry gel was pressed into a pellet having ø14 and a thickness of 2 mm under pressure of 2 t/cm2using a static compressor. The pellet was put in an alumina boat and heated at 750° C. for 48 hours in an atmosphere of oxygen in a tube furnace, and pulverized in a mortar to obtain powdery LiNi 0.789Co0.151Al0.051O2.
- The respective powder X -ray diffraction patterns of the complex oxides obtained in Examples 5, 6 and 7 are shown in FIGS. 4, 5 and6. As is apparent from them, any peak based on by-product was not recognized in each process and the complex oxides are estimated to have uniformly doped layered structure.
- Furthermore, the ratio of the trivalence in (Ni+Co) and the physical properties such as BET specific surface area, the peak intensity ratios (003)/(104) and (006)/(101) obtained by powder X -ray diffraction and the bulk density, each measured with respect to these complex oxides are shown in table 4. A SEM photograph (×30,000 magnifications) indicating the primary particles of the complex oxide of Example 5 is shown in FIG. 7, that (× 30,000 magnifications) indicating the primary particles of the complex oxide of Example 6 in FIG. 8 and that (× 10,000 magnifications) indicating the primary particles of the complex oxide of Example 7 in FIG. 9. The scale unit of —line shown in the lower part of the respective photographs indicates 1 μm.
- The trivalent (Ni+Co) ratio and the BET specific surface area were measured according to Experimental Examples 2 and 3, respectively.
TABLE 4 Ratio Bulk of the Density Trivalence Particle in (Ni + Co) BET Ratio of Ratio of Size No. (%) m2/g (003)/(104) (006)/(101) (g/ml) Example 5 100 0.43 1.466 0.115 1.75 Example 6 99.7 0.68 1.557 0.111 2.24 Example 7 99.2 0.61 1.351 0.119 2.21 - As is apparent from table 4, the trivarent (Ni+Co) ratio is approximately 100% and the peak intensity ratio of (003)/(104) obtained by the powder X - ray diffraction is lower than 1.2 while that of (006)/(101) is higher than 0.13 and thus the degree of crystallization is exceedingly high. Furthermore, it can be seen from the SEM photographs that the primary particle grow to a great extent and the bulk density became sufficently high in case of the complex oxides of Examples 6 and 7 each subjected to press molding.
- There was prepared a mixed aqueous solution of 2.0 mol/l nickel nitrate, cobalt nitrate and aluminum nitrate wherein the molar ratio of Ni:Co:Al was 790:165:25. This mixed aqueous solution and 1.0 mol/l aqueous sodium hydroxide solution were simultaneously added at 25° C. under vigorous stirring so as to keep pH to 10.0 therby effecting the continuous reaction.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.79Co0.165Al0 025(OH)1 845(NO3) 0.14·0.2 H2O) and suspended in water. Thereafter, boric acid was added to the suspension in an amount such that the molar ration of Ni:Co:Al:B became 790:165:25:20 with respect to the Ni, Co and Al contents in the suspension. To the resultant slurry was added dropwisely a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Al+B) was 1.05. Thereafter, the reaction mixture was spray-dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company) and then pulverized in a mortar to obtain powdery LiNi0 79 0Co0.165Al0.025B0.020O2.
- There was prepared a mixed aqueous solution of 2.0 mol/l nickel nitrate, cobalt nitrate and aluminum nitrate wherein the molar ratio of Ni:Co:Al was 790:140:50. This mixed aqueous solution and 1.0 mol/l aqueous sodium hydroxide solution were simultaneously added so as to keep pH to 9.75 at 25° C. under vigorous stirring, thereby effecting the continuous reaction.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.79Co0.14Al0.05(OH)1.86(NO3)0.15·0.24H2O) and suspended in water. Thereafter, boric acid was added to the suspension in an amount such that the molar ration of Ni:Co:Al:B became 790:140:50:20 with respect to the Ni, Co and Al contents in the suspension. To the resultant slurry was added dropwisely a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Al+B) was 1.05. Thereafter, the reaction mixture was spray - dried. The obtained dry gel was put in an alumina boat and heated at 775° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company) , and then pulverized in a mortar to obtain powdery LiNi0 79 0Co0.140Al0.050B0.020O2.
- There was prepared a mixed aqueous solution of 2.0 mol/l nickel nitrate, cobalt nitrate and aluminum nitrate wherein the molar ratio of Ni:Co:Al was 790:90:100. This mixed aqueous solution and 1.0 mol/l aqueous sodium hydroxide solution were simultaneously added so as to keep pH to 9.5 at 25° C. under vigorous stirring thereby effecting the continuous reaction.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.79Co0.09Al0.10(OH)1.92(NO3)0.14·0.18 H2O) and suspended in water. Thereafter, boric acid was added to the suspension in an amount such that the molar ration of Ni:Co:Al:B became 790:90:100:20 with respect to the Ni, Co and Al contents in the suspension. To the resultant slurry was added dropwisely a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Al+B) was 1.05. Thereafter, the reaction mixture was spray - dried. The obtained dry gel was put in an alumina boat and heated at 775° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company) , and then pulverized in a mortar to obtain powdery LiNi0 79 0Co0.090Al0.100B0 020O2.
- There was prepared a mixed aqueous solution of 2.0 mol/l nickel nitrate, cobalt nitrate, aluminum nitrate and ferric nitrate wherein the molar ratio of Ni:Co:Al:Fe was 800:100:50:50. This mixed aqueous solution and 1.0 mol/l aqueous sodium hydroxide solution were simultaneously added so as to keep pH to 9.5 at 25° C. under vigorous stirring thereby effecting the continuous reaction.
- The obtained reaction product was filtered, washed with water (the portion was dried after washing and its composition was Ni0.8Co0.01Al0 05Fe0 05(OH)1 96NO3) 0.14·0.18 H2O) and suspended in water to form a slurry. To the resultant slurry was added dropwisely a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Al+Fe) was 1.05. Thereafter, the reaction mixture was spray-dried. The obtained dry gel was put in an alumina boat and heated at 725° C. for 15 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company) , and then pulverized in a mortar to obtain powdery LiNi0.80 0Co0.100Al0.050Fe0.050O2.
- There was prepared a mixed aqueous solution of 2.0 mol/l nickel nitrate, cobalt nitrate and manganese nitrate wherein the molar ratio of Ni:Co:Mn was 800:150:50. This mixed aqueous solution and 1.0 mol/l aqueous sodium hydroxide solution were simultanuously added so as to keep pH to 9.0 at 25° C. under vigorous stirring thereby effecting the continuous reaction.
- The obtained reaction product was filtered, washed with water and suspended in water to form a slurry. To the resultant slurry was added dropwisely a 3.0 M aqueous lithium hydroxide solution in an amount such that the atomic ratio of Li/(Ni+Co+Mn) was 1.05. Thereafter, the reaction mixture was spray-dried. The obtained dry gel was put in an alumina boat and heated at 750° C. for 10 hours in an atmosphere of oxygen in a tube furnace (TF-630 type, a product of Yamada Electric Company), and then pulverized in a mortar to obtain powdery LiNi0.800Co0.150Mn0.050O2.
- 1.00 Mol lithium hydroxide, 0.80 mol nickel hydroxide, 0.10 mol cobalt hydroxide and 0.01 mol aluminum hydroxide were sufficiently mixed in dry state and pulverized in a mortar, and then pelletized into size of 14 mm of a diameter×2 mm of a thickness. The resultant pellets were heated at 750° C. for 48 hours in an atmosphere of oxygen.
- The chemical composition of the heating product was LiNi0.80Co0.10Al0.10O2.
- 1.00 Mol lithium hydroxide, 0.79 mol nickel hydroxide, 0.165 mol cobalt hydroxide, 0.025 mol aluminum hydroxide and 0.02 mol boric acid were sufficiently mixed in dry state and pulverized in a mortar, and then pelletized into size of 14 mm of a diameter×2 mm of a thickness. The resultant pellets were heated at 750° C. for 48 hours in an atmosphere of oxygen.
- The chemical composition of the heating product was LiNi0.79Co0.165Al0.025B0.02O2.
- The powder X - ray diffraction patterns of the complex oxides obtained in Examples 8˜11 are shown in FIGS.10˜ 13, respectively. As is apparent from them, any peak based on by-product was not recognized in each process and the complex oxides are estimated to have uniformly doped layered structure.
- Furthermore, the trivalent (Ni+Co) ratio and the physical properties such as BET specific surface area, the peak intensity ratios (003)/(104) and (006)/(101) obtained by powder X -ray diffraction, each measured with respect to these complex oxides are shown in table 5. A SEM photograph (×1,500 magnifications) indicating the primary particles of the complex oxide of Example 8 is shown in FIG. 14, that (×1,500 magnifications) indicating the primary particles of the complex oxide of Example 10 is shown in FIG. 15 and that (×1,500 magnifications) indicating the primary particles of the complex oxide of Example 11 is shown in FIG. 16. The scale unit of—line shown in the lower part of the respective photographs indicates 10 μm.
- The trivalent (Ni+Co) ratio and the BET specific surface area were measured according to Experimental Examples 2 and 3, respectively.
TABLE 5 Ratio of the Trivalence in (Ni + Co) BET Ratio of Ratio of No. (%) m2/g (003)/(104) (006)/(101) Example 8 100.0 0.44 1.330 0.105 Example 9 100.0 0.62 1.236 0.102 Example 10 99.8 0.57 1.311 0.114 Example 11 99.9 0.69 1.334 0.099 - As is apparent from table 5, each of the complex oxides of the above Examples has the physical property satisfying sufficiently the range defined in the appended claims.
- Moreover, table 6 shows the results of the battery test (charge and discharge test) conducted according to Experimental Example 4 using the respective complex oxides of Examples 5˜11 and Comparative Examples 4˜5 to evaluate initial discharge capacity (mAh/g), discharge capacity at 100th cycle (mAh/g) and decrease rate of discharge capacity at 100th cycle (%).
TABLE 6 Initial Decrease Rate of Discharge Discharge Capacity Discharge Capacity Capacity at 100th Cycle at 100th Cycle No. (mAh/g) (mAh/g) (%) Example 5 173 161 7.2 Example 6 176 165 6.4 Example 7 176 165 6.0 Example 8 185 177 4.3 Example 9 186 180 3.2 Example 10 176 169 4.2 Example 11 159 147 7.6 Comparative 148 111 24.7 Example 4 Comparative 139 98 29.6 Example 5 - It is recognized from table 6 that the lithium nickel cobalt complex oxides have a tendency to decrease the initial discharge capacity with the increase in the Al content therein and correspondingly with decrease in the Co content as compared with the complex oxide of the Comparative Example 3 shown in table 3, and that the improvement in the cycle characteristics may be achieved by the addition of boron. Furthermore, it is understood that the addition of Fe shows a great tendency to decrease the initial discharge capacity as compared with the case of Al addition. However, the complex oxide of the present invention is superior in the initial capacity and the cycle characteristics to those of the Comparative Examples 4 and 5.
- It can be seen from the above results that although the addition of Al has a significance in respect of making the amount used of the expensive Co decreased, it causes minus effect in the battery performance. However, the positive electrode employed hitherto as the material for lithium ionic secondary battery have a problem of the thermal stability. On the other hand, the complex oxides obtained by the present invention cause a good improvement effect with respect to the thermal stability.
- As an index for the thermal stability of the positive electrode material, there is a means wherein differential thermal analysis is conducted with respect to the positive electrode material placed in charged state and the exothermic temperature at which oxygen evolution occurs is measured. Then, the test results of the thermal stability test carried out according to Experimental Example 5 with respect to the complex oxides obtained by the present invention are shown in table 7.
TABLE 7 Exothermic Peak Temperature at which No. Oxygen Evolution Occurs (° C.) Example 1 215 Example 2 212 Example 3 218 Example 4 220 Example 5 236 Example 6 253 Example 7 253 Example 8 252 Example 9 249 Example 10 236 Comparative 198 Example 2 - It can be seen from table 7 that the introduction of Al into the lithium nickel cobalt complex oxide causes the elevation in the exothermic temperature at which oxigen evolution occurs in comparison with the complex oxide of Comparative Example 2, and further large primary particle as in Examples 6 and 7 causes the elevation in the exothermic temperature similarly so that the thermal stability can be improved.
- As stated above, the lithium nickel cobalt complex oxide of the present invention, especially one doped completely with Al and/or B as the solid liquid is satisfactory secondary battery positive electrode material as the battery performance.
- Scherrer's method:
- It is a method wherein the size of crystallite is calculated by the following equation (1) on the assumption that the width of diffraction pattern is dependent on the size of crystallite alone owing to uniformity in the size of crystallite and no strain in the crystals.
- D h k l=(kλ)/(βcosθ) (Equation 1)
- wherein Dh k l (angstrom) represents size of crystallite in vertical direction to the face (hkl), A (angstrom) the wave length of X-ray, G (rad) the width of diffraction pattern, θ (° ) angle of diffraction, and k a constant.
- A method for measuring trivalent (Ni+Co):
- The trivalent (Ni+Co) ratio is value expressed in percentage the ratio of the trivalent (Ni+Co) to the total (Ni+Co), and is measured by oxidation-reduction titration. 0.2 Gram of a sample was dissolved in 0.25 M FeSO4-3.6 N H2SO4 solution, and 2 ml of a concentrated phosphoric acid was added to the solution. The mixture was titrated with a 0.1 N KMnO4 solution. Blank test was carried out in the same manner as in the above. The trivalent (Ni+Co) % was calculated by the following equation. In the equation, f represents the factor of the 0.1 N KMnO4 solution, X0 the titer of the blank test (ml) , X the titer of the sample (ml), m the amount of the sample (g), A the content of Ni (%) and B the content of Co (%) The trivalent (Ni+Co) ratio (%) in the sample=10f ( X0−X)/m (A/5.871+B/5.893)
- A method for measuring BET specific surface area:
- The sample was degassed by heating under the flow of a mixed gas of 30% nitrogen and, 70% helium, and thereafter specific surface area was measured according to the BET one point continuous flowing method using “MONOSORB” (a product of Yuasa Ionics Co., Ltd.).
- A battery test method
- The lithium nickel complex oxide, acetylene black as a conductive agent and tetrafluoroethylene as a binder were mixed in a ratio of 88:6.0:6.0% by weight. Thereafter, the mixture was subjected to compression molding on stainless steel mesh, thereby obtaining pellets each having a diammeter of 18 mm. The resultant pellets were dried at 200° C. for 2 hours, and used as a positive electrode material.
- As a negative electrode material was used a rolled lithium metal sheet pressed-bonded to a stainless substrate. As a diaphragm, porous membrane made of polypropylene (“Cell Guard 2502”) and a glass filter-paper filter were used. There was used an electrolyte in which 1 M LiClO4 was dissolved in an ethylene carbonate/dimethylmeth oxyethane mixture (1:1 weight ratio). The procedures up to completion from setup of a test cell (semi-open type cell) were conducted in an argon replaced dry box. The charging and discharging for this lithium battery were performed under a voltage control between 3.0 V and 4.3 V at a constant current density of 0.4 mA/ cm2.
- A thermal stability test method:
- A cell was prepared by a similar manner as in Experimantal Example 3 and charging was conducted under the constant current density of 0.4 mA/cm3 until it reached 4.4 V. After the completion of charging, the cell was decomposed to take out the positive electrode. The positive electrode was washed with the electrolyte solution and dried under vacuum. The dried positive electrode was subjected to a differential thermal-analysis apparatus under flow of nitrogen at a heating rate of 2° C./min. to examine the exothermic peak temperature at which oxygen evolution occurs.
- Industrial Applicability:
- As explained above, according to the present invention there can be provided a novel complex oxide which may be represented by the general formula (I)
- LiyNi1-xCox1Mx2O2 (I)
- and which is a positive electrode active material for a secondary battery which is excellent in the charging and discharging cycle characteristics so that it retaines high battery capacity that is comparable to the hitherto known LiNiO2 even by increasing the number of cycle and which has an improved cycle property (stability) at high temperature.
- Also, since the amount used of the expensive Co can be suppresed to the minimum by introducing further the metal represented by M, it is advantageous from the viewpoint of cost.
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PCT/JP1997/002803 WO1998006670A1 (en) | 1996-08-12 | 1997-08-11 | Lithium/nickel/cobalt composite oxide, process for preparing the same, and cathode active material for rechargeable battery |
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WO1998006670A1 (en) | 1998-02-19 |
CA2263320C (en) | 2006-08-08 |
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CN1232438A (en) | 1999-10-20 |
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US6395250B2 (en) | 2002-05-28 |
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